M-MOF-74吸附分离H2/He混合物的分子模拟研究

doi:10.11949/0438-1157.20220531

摘要/Abstract

摘要：

为了探究有机金属框架MOF-74能否作为一种优良的固体吸附剂，分离H₂/He混合物中H₂，并达到提纯He的目的，采用分子模拟的手段研究了H₂、He及H₂/He混合物在M-MOF-74（M=Mg、Co、Ni、Cu、Zn）上的吸附性能及吸附机理。结果表明，在1 bar（1 bar=10⁵ Pa）压力和25℃条件下，纯H₂对纯He在Ni-MOF-74上的选择性达6.58，而Mg-MOF-74对H₂的吸附量最大，其值为0.19 mmol·cm^-3，为He吸附量的6.46倍。当H₂/He混合物的浓度发生变化时，对其在M-MOF-74上的吸附分离因子没有较大影响，说明浓度变化不会影响M-MOF-74上吸附位点容纳H₂和He的能力。吸附位点和吸附热分析表明，MOF-74上的金属离子未饱和位点能够显著增强其对H₂的吸附能力。其结果对判断M-MOF-74是否具有分离H₂/He混合物的潜力，以及定量分析MOFs金属未饱和位点对H₂/He混合物分离的贡献提供了一定的理论基础。

关键词: MOF-74, H₂/He混合物, 吸附剂, 吸附, 分子模拟

Abstract:

In order to explore whether the organometallic framework MOF-74 can be used as an excellent solid adsorbent to separate H₂ in H₂/He mixture and achieve the purpose of purifying He, the adsorption performance and adsorption mechanism of H₂, He and H₂/He mixture on M-MOF-74 (M=Mg, Co, Ni, Cu, Zn) were studied by molecular simulation. The results show that the selectivity of pure H₂ to pure He on Ni-MOF-74 is 6.58 under the conditions of 1 bar pressure and 25 °C. The amount of H₂ adsorbed on Mg-MOF-74 is the largest (0.19 mmol·cm^-3) in the same condition, which is 6.46 times of He. When the concentration of the H₂/He mixture was changed, it had no great effect on its adsorption separation factor on M-MOF-74, indicating that the concentration change would not affect the ability of the adsorption sites on M-MOF-74 to accommodate H₂ and He. The adsorption site and adsorption heat analysis showed that the metal ion unsaturated sites on MOF-74 could significantly enhance its adsorption capacity for H₂. The results provide a theoretical basis for judging whether M-MOF-74 has the potential to separate H₂/He mixtures and quantitatively analyzing the contribution of metal unsaturated sites of MOFs to the separation of H₂/He mixtures.

Key words: MOF-74, H₂/He mixture, adsorbents, adsorption, molecular simulation

中图分类号:

TQ 028.8

王玉杰, 李申辉, 赵之平. M-MOF-74吸附分离H₂/He混合物的分子模拟研究[J]. 化工学报, 2022, 73(10): 4507-4517.

Yujie WANG, Shenhui LI, Zhiping ZHAO. Molecular simulation study on adsorption and separation of H₂/He mixtures by M-MOF-74[J]. CIESC Journal, 2022, 73(10): 4507-4517.

图/表 11

表1 M-MOF-74的结构特点

Table 1 Structural features of M-MOF-74

名称	CSD号	孔径/nm	孔隙率/%	比表面积/(m²·m^-3)	晶胞参数/nm；(°)
Mg-MOF-74	1863524	1.1	0.724	1943.2	2.6×2.6×0.69；90×90×120
Co-MOF-74	1494752	1.1	0.721	1818.5	2.6×2.6×0.67；90×90×120
Ni-MOF-74	1494751	1.1	0.725	1834.4	2.6×2.6×0.67；90×90×120
Cu-MOF-74	—	1.1	0.722	1878.8	2.6×2.6×0.69；90×90×120
Zn-MOF-74	1863522	1.1	0.723	1922.4	2.6×2.6×0.69；90×90×120

图1 （a）M-MOF-74的结构;（b）H2和He的分子尺寸;（c）H2的五点模型; (d) M-MOF-74对H2的吸附等温线(其中Exp代表实验测得的吸附等温线，数据来自文献[36-38]; Sim代表本文模拟得到的数据; 1? =0.1 nm)

Fig.1 (a) Structure of M-MOF-74; (b) Molecular dimensions of hydrogen and helium; (c) Five-point model of hydrogen; (d) Adsorption isotherms of H2 in M-MOF-74 (where Exp represents the experimentally measured adsorption isotherm, and the data are from Refs. [36-38]; Sim represents the data get from the simulation of this work)

表2 H2与He的物化性质

Table 2 Physicochemical properties of H2 and He

名称	临界温度/K	临界压力/bar	分子动力学直径/nm	极化率/(10^-25 cm³)	电四极矩/(10^-40 C·m^-2)	摩尔质量/(g·mol^-1)
He	5.2	2.28	0.260	2.08	0	4.003
H₂	33.2	13.15	0.289	7.87	2.21	2.016

表3 M-MOF-74的力场参数及原子电荷

Table 3 Force field parameters and atomic charges of M-MOF-74

名称	势陷深度ε/K	平衡距离σ/nm	原子电荷q/e
名称	势陷深度ε/K	平衡距离σ/nm	Mg	Co	Ni	Zn	Cu
Mg	55.857	0.260	1.678
Co	7.045	0.255	1.420
Ni	7.545	0.252	1.501
Zn	62.399	0.246	1.492
Cu	2.516	0.311	1.128
C1	47.856	0.347	0.93030	0.93940	0.88260	0.87980	1.14250
C2	47.856	0.347	-0.48150	-0.52700	-0.44910	-0.26750	-0.53740
C3	47.856	0.347	0.46750	0.49000	0.44070	0.40420	0.55200
C4	47.856	0.347	-0.38240	-0.40320	-0.43910	-0.37410	-0.33180
O1	48.158	0.303	-0.87140	-0.79450	-0.78000	-0.82960	-0.76640
O2	48.158	0.303	-0.76800	-0.58940	-0.66470	-0.75710	-0.72140
O3	48.158	0.303	-0.80540	-0.72910	-0.71650	-0.77420	-0.68620

表4 本文计算得到的吸附热与实验值的对比

Table 4 Comparison of heat of adsorption calculated in this work with experimental values

文献	H₂吸附热/(kJ·mol^-1)
文献	Mg- MOF-74	Co- MOF-74	Ni- MOF-74	Cu-MOF-74	Zn-MOF-74
[32]	-10.1	-10.7	-12.9	—	-8.8
[33]	-10.3	—	—	—	—
[34]	—	—	—	—	-8.8
[35]	—	—	—	—	-8.3
本文	-10.41	-10.44	-11.71	-8.41	-9.17

图2 环境压力对H2及He在M-MOF-74上吸附量和选择性的影响

Fig.2 Effects of ambient pressure on the adsorption of H2 and He on M-MOF-74

图3 H2/He混合浓度对两者在M-MOF-74上吸附量和分离因子的影响

Fig.3 The effect of H2/He mixture concentration on the adsorption of H2 and He on M-MOF-74

图4 M-MOF-74上OMS位点对H2和He在M-MOF-74上吸附量及H2/He选择性的影响

Fig.4 Effects of OMS sites on M-MOF-74 on the adsorption capacity of H2 and He and ideal selectivity of H2/He on M-MOF-74

图5 H2、He在M-MOF-74上的吸附热分布

Fig.5 Adsorption heat map of H2 and He in M-MOF-74

图6 H2、He在M-MOF-74上的吸附热频率直方图

Fig.6 Histograms of adsorption heat frequencies of H2 and He on M-MOF-74

图7 （a）H2在M-MOF-74上的金属离子吸附位点及RDG分析(其中蓝色代表一定的配位作用，绿色代表弱的范德华相互作用)，等值面为0.2；（b）H2在M-MOF-74上的苯环吸附位点;（c）H2和He到M-MOF-74的平衡距离;（d）H2和He与M-MOF-74的结合能

Fig.7 (a) Metal ion adsorption sites and RDG analysis of H2 on M-MOF-74 (Blue represents certain coordination and green represents weak van der Waals interactions), isosurface at 0.2; (b) H2 adsorption sites on the benzene ring on M-MOF-74; (c) Equilibrium distances of H2 and He to M-MOF-74; (d) Binding energy of H2 and He to M-MOF-74

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M-MOF-74吸附分离H₂/He混合物的分子模拟研究

Molecular simulation study on adsorption and separation of H₂/He mixtures by M-MOF-74

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